Waterinsoluble azodyestuffs



Patented Feb. 11, 1936 WEE ' hdiddz'l @FFHQE and Werner Zerweck,Frankfort-on-the-ll iain- Fechenheim, Germany, assignors to GeneralAniline Works, inc, New York, N. $2., a corporation oi Delaware NoDrawing. Qriginal application September 2,

1933, Serial No. 688,06). Divided and this application August 4, 1934,Serial No. 738,562.

Germany September 8 Claims.

The present invention relates to waterinsoluble azodyestuiis and tofibres dyed therewith, more particularly it relates to dyestuffs oi thegeneral formula:

wherein T stands for the radical of a thiazole compound free from agroup inducing solubility in water, such as the sulfonic or carboxylicacid group, that means T may stand for a thiazole nucleus which may bearnon-solubilizing monovalent substituents, such as alkyl, alkoxy,halogen, the nitro group, the amino group, a substituted amino group,such as alkylor acylamino; furtherTmayrepresent a thiazole nucleus towhich an arylene radical is condensed, for instance, T may stand for theradical of the thiazole which is derived from an aminobenzene,aminonaphthalene, aminocarbazcle, aminodiphenyleneoxide,aminodiphenylenesulfide, aminoacenaphthene, aminofiuorenone,aminofiuorene, aminocumarane, which amino compounds may bearnon-solubilizing substituents, R stands for the radical of a diazotizedprimary amine suitable for producing an azodyestuff free from a groupinducing solubility in water, for instance, for a radical of the benzeneor naphthalene series free from a sulfonic or carboxylic acid groupwhich may bear as substituent, for instance, halogen, alkyl, alkoxy, thenitro group and a substituted amino group, and wherein ac stands for anacyl radical, such as an acyl of the aliphatic or aromatic series, forinstance, for acetyl, propionyl, butyryl, benzoyl, chlorobenzoyl,methylbenzoyl, nitrobenzoyl and the like.

Our new dyestuffs are obtainable by diazotizing a diazotizationcomponent free from a group inducing solubility in water and coupling insubstance or on a substratum, especially the vegetable fibre, with acoupling component of the 45 general formula:

(Cl. 26il44.2)

processes, generally yield yellow to yellowishbrown shades of goodfastness properties.

As is known from literature that Z-aminoarylenethiazoles may react inthe imino form, we include in our invention those dyestuffs containingthe coupling component in the imino form and which may be represented bythe probable general formula:

wherein the figures T, R and ac mean the same as stated above.

The coupling components used in the manufacture of our new dyestuffshave been described in our parent application for Letters Patent Ser.No. 688,060, filed September 2, 1933,

The invention is illustrated by the following examples, without beinglimited thereto:

Example 1.6 grams of 2-acetoacetylamino-6- ethoxybenzothiazole aredissolved with 5 cc. of aqueous caustic soda lye of 38 Be. strength and10 cc. of Turkey red oil and water to one litre. To this solution somecommon salt is added, and 50 grains of cotton yarn are impregnated inthis bath for hour. The impregnated yarn is squeezed and introduced forabout /2 hour into a developing bath of one litre containing 1.42 gramsof diazotized 1-amino-2-methyl-5-chlorobenzene, said developing bathhaving previously been neutralized by the addition of sodium acetate.The cotton yarn is rinsed, soaped in a boiling bath, rinsed again anddried. A clear yellow is thus obtained having excellent fastnessproperties and being dischargeable to a pure white. The dyestuifcorresponds to the following formula:

Example 2.5O grams of cotton yarn are impregnated as described inExample 1. On developing in a developing bath of one litre containing1.52 grams of diazotized l-amino-2-nitro-4- methylbenzene, there isobtained after rinsing and soaping a reddish-yellow of good fastnessproperties. The dyestufi corresponds to the following formula:

CHs

Example 4.50 grams of cotton yarn are impregnated as described inExample 1. On developing in a developing bath of one litre containing1.27 grams of, diazotized l-amino-Z-chlorobenzene, there is obtainedafter rinsing and soaping a clear greenish-yellow of good fastnessproperties and good dischargeability. The dyestuif corresponds to thefollowing formula:

Example 5.--50 grams of cotton yarn are impregnated as described inExample 1. On developing in a developing bath of one litre containing2.2 grams of diazotized 2-amino-4-chlorodiphenylether, there is obtaineda clear yellow which can be discharged to a pure white. The dyestuffcorresponds to the following formula:

Example 6.7 grams of 2-acetoacetylamino-6- methoxybenzothiazole aredissolved in the usual manner with the aid of aqueous caustic soda lye,Turkey red oil and some Water, and the solution is made up with water toone litre. To the solution some Glaubers salt is added, and 50 grams ofcotton yarn are impregnated in this: bath for hour, then rinsed andintroduced for about hour into a developing bath containing in one litre1.68 grams of diazotized l-amino-Z-nitrol-methoxybenzene. After rinsing,soaping, again rinsing and drying, there is obtained a goldenyellow ofgood fastness properties. The dyestufi corresponds to the followingformula:

OCH:

By substituting the 2 acetoacetylamino 6 methoxybenzothiazole by acorresponding quantity of 2benzoylacetylamino-6-methoxybenzothiazole,there is obtained a dyestuff having similar properties.

Example 7.-5 grams of 2-acetoacetylamino-6- benzoylamino-benzothiazoleare dissolved in the usual manner with the aid of aqueous caustic sodalye, Turkey red oil and some water, and made up with water to one litre.To the solution some Glaubers salt is added, and 50 grams of cotton yarnare impregnated in this bath for /2 hour, then rinsed and introduced forabout /2 hour into a developing bath of one litre containing 1.42 gramsof diazotized 1-amino-2-methyl- 4-chlorobenzene, rinsed, soaped in aboiling bath, rinsed and dried. A greenish-yellow is thus obtained whichcan be discharged to a pure white. The dyestufi corresponds to thefollowing formula:

It s it OCH:

By substituting the 1-amin0-2-methyl-4-chlorobenzene by1-amino-2-methyl-5-chlorobenzene, there is obtained a dyestufl ofsimilar properties.

Example 8.34= grams of 2-benzoy1acetylamino-6-ethoxybenzothiazole aredissolved in 300 grams of pyridine; thereto is added an aqueous solutioncontaining 14.2 grams of diazotized 1- amino-2-methyl-5-chlorobenzenewhich has been neutralized by the addition of sodium acetate, withcooling. When the coupling is complete, the reaction liquor is poured.into water, and the dyestuif which separates in form of yellow flakes isfiltered. After drying, it is a reddish-yellow powder.

Example 9.--1.39 grams of 2-acetoacetylamirio- G-ethoxybenzothiazole and1.2 grams of the diazoamino compound from diazotized -chloro-2- methyl-1aminobenzene and sarcosine are pasted with 0.7 cc. of aqueous causticsolution of 38 B. strength, 5 grams of neutral chromate solution and 5grams of thiodiglycol, and the paste is dissolved in 25 cc. of Water.The solution is stirred into 50 grams of neutral starchtragacanththickener and made up with water to 100 grams. With this paste cottontissue is printed, the cotton is dried and the dyestufi is developed bythe action of steam containing acetic or formic acid. A cleargreenish-yellow is thus obtained. The dyestuff is identical with thatdescribed in Example 1.

Example 10.1.39 grams of 2-acetoacetylamino-G-ethoxy-benzothiazole and2.05 grams of the diazoamino compound from diazotized i-nitro-2-methoxy-l-aminobenzene and 1-methylaminobenzene-Z-carboxylicacidl-sulfonic acid are pasted with 0.7 cc. of aqueous caustic soda lyeof 38 B. strength, 5 grams of neutral chromate solution and 5 grams ofthiodiglycol, and the paste is dissolved in 25 cc. of water. Thesolution is stirred into 50 grams of neutral starchtragacanth thickenerand made up with water to 100 grams. With this paste cotton tissue isprinted, the cotton is dried, and the dyestuff is developed by theaction of steam containing acetic or formic acid. A clear golden-yellowis thus obtained. The dyestuff corresponds to the following formula:

Example 11.50 grams of cotton yarn are impregnated as described inExample 1. On developing in a developing bath of one litre containing2.17 grams of diazotized l-aminopyrene, there is obtained after rinsing,soaping, rinsing and drying, a powerful yellowish-brown. The dyestuffcorresponds to the following formula:

Example 12.-6 grams of 2acetoacetylamino-(9-ethyl-2',3-carbazole)-thiazole are dissolved in hot water with 6 cc.of aqueous caustic soda lye of 38 Be. and 6 cc. of Turkey red oil to 1litre. Some common salt is added, and in this bath 5i) grams of cottonyarn are impregnated for hour. The yarn is squeezed and introduced forabout hour into a developing bath of one litre containing 1.42 grams of1amino-2methyl-4- chlorobenzene. After rinsing; soaping in a boil ingbath, again rinsing and drying, there is obtained a clear golden yellowof good fastness properties. The dyestufi corresponds to the followingformula:

| N C2 5 I Example 13.-6 grams of acetoacetylamino- (3,4-acenaphthene)-thiazole are dissolved in hot Water with 5 cc. of aqueous caustic sodalye of 38 B. and cc. of Turkey red oil to one litre. 50 grams of cottonyarn are impregnated in this solution, and the dyeing is developed byintroducing for hour into a developing bath containing 1.42 grams ofdiazotized 1-amino-2- methyl-5-chlorobenzene. After rinsing, soaping,again rinsing and drying, there is obtained an orange of good fastnessproperties. The dyestuif corresponds to the following formula:

Example 14.3.24 grams of the acetoacetyl compound of the formula:

are dissolved in 50 cc. of pyridine, and thereto is added a diazosolution prepared from 1.42 grams of l-amino-Z-methyl-4-ch1orobenzene. Areddish-yellow dyestuif is thus obtained suitable for dyeing lacquers.

Example 15.1.42 grams of 2-acetoacetylamino-(1,2-naphtho)-thiazole and1.28 grams of the diazoamino compound from diazotized 4-chloro-Z-methoxy-l-arninobenzene and sarcosine are made into a pastewith 0.7 cc. of aqueous caustic soda lye of 38 B. strength, 5 grams ofneutral chro-mate solution and 5 grams of thiodiglycol, and the paste isdissolved in cc. of Water. The solution is stirred into 50 grams ofneutral starchragacanth thickener and made up with water to 106 grams.With this paste cotton tissue is printed, the cotton is dried, and thedyestuff is developed by the action of steam containing acetic acid orformic acid. A clear greenish-yellow is thus obtained. The dyestuffcorresponds to the following formula:

H N I Example 16.--1.42 grams of2-aoetoacetylamino-(2,l-naphtho)-thiazole and 2.05 grams of thediazoamino compound from diazotized 4- nitro-2-methoxy-l-aminobenzeneand l-methylaminobenzene-Z-carboxylic acidl-sulfonic acid, yield, whenprinted and developed as described in Example 15, a powerful yellow. Thedyestufi corresponds to the following formula:

Example 17.3 grams of 2-acetoacetylamino- (2,1'naphtho) -thiazole aredissolved with 3 cc. of ethylalcohol, 4.5 cc. of aqueous caustic sodasolution of 38 B. strength and 6 cc. of Turkey red oil in hot Water toone litre. Some common salt is added to this solution, 50 grams ofcotton yarn are impregnated therewith for about hour, and the dyeing isdeveloped by introducing the cotton yarn into a developing bath of onelitre containing 2.6 grams of diazotizedl-methoXy-2-aminobenzene-4-sulfodiethy1amide. After rinsing, soaping ina boiling bath, again rinsing and drying, there is obtained a cleargreenishyellow of excellent fastness to light. The dyestuff correspondsto the following formula:

Example 18.3 grams of 2-acetoacety1amino- 6 -methoxy-(1' ,2 -naphtho)-thiazo1e are dissolved with 6 cc. of aqueous caustic soda lye of 38 B.and 6 cc. of Turkey red oil in hot water to one litre. To the solutionsome common salt is added, and 50 grams of cotton are impregnated in thebath for hour. By developing in a developing bath of one litre,containing 2.2 grams of diazotized l-chloro-2-aminodiphenylether, thereis obtained after rinsing, soaping, again rinsing and drying a clearyellow of good fastness properties. The dyestufi corresponds to thefollowing formula:

In an analogous manner the dyestuff from 2- acetoacetylamino-(1',2'-na-phtho) thiazole and diazotized l-amino 2 nitro-l-methoxybenzeneyields a clear golden-orange of very good fastness properties. Thedyestufi corresponds to the following formula:

In an analogous manner the dyestuif from 2-acetoacetylamino-4-methylthiazole and diazotized2-methoxy-4-nitro-l-aminobenzene yields a powerful reddish-yellow. Thedyestuif corre- In an analogous mannerZ-benzoylacetylamino-l-methylthiazole and diazotized 4-chloro-2-methyl-l-aminobenzene yield a powerful greenish-yellow of good fastnessproperties. The dyestuff corresponds to the following formula:

In an analogous manner Z-acetoacetylamino- 4-rphenylthiazole anddiazotized 4-methoXy-2- nitro-l-aminobenzene yield a golden-orange ofvery good fastn'ess to light. The dyestuif corresponds to the followingformula:

HsCa-C-N O-NH-C o-oH-o -0113 HOS II N In an analogous manner2-acetoacetylamino- 4,5-diphenylthiazole and diazotized2-methoxysulfodiethylamido l aminobenzene yield a greenish-yellow whichcan be discharged to a pure white. The dyestuff corresponds to thefollowing formula:

In an analogous manner Z-acetoacetylamino- 4,5-diphenylthiazole anddiazotized 2-ch1oro-5- trifluoromethyl-l-aminobenzene yield areddishyellow which can be discharged. The dyestuff corresponds to thefollowing formula:

In an analogous manner 2-acetoacetylamino-6- exthoxybenzothiazole anddiazotized Z-methoxy-3-aminofluorenone yield a powerful yellow. Thedyestuff corresponds to to the following formula:

In an analogous manner Z-acetoaoetylaminofi-ethoiiybenzothiazole anddiazotized 'bt-naphthylamine yield a powerful yellow. The dyestuffcorresponds to the following formula:

This is a division of application Serial No. 688,060, filed September 2,1933.

We claim:

1. Waterins-oluble azodyestuffs ofthe general formula:

wherein T stands for the radical of a thiazole compound, ac stands foran acyl radical and R stands for .the radical of a diazotized primaryamine suitable for producing azodyestuffs, yielding, when produced onthe fibre, generally yellow shades of good fastness properties.

2. Waterinsoluble azodyestufis of the general formula:

wherein T stands for the radical of a thiazole compound, R stands for aradical of the aliphatic or aromatic series and R stands for the radicalof a diazotized primary amine suitable for producing azodyestufis,yielding, when produced on the fibre, generally yellow shades of goodfastness properties.

3. Waterinsoluble azodyest'uffs of the general formula:

yielding, when produced on the fibre, clear greenish-yellow shades ofgood fastness properties and 7. Fibre dyed with a dyestuff as claimed indischargeability. claim 3.

5. Fibre dyed with a dyestuff as claimed in 8. Fibre dyed with thedyestufi as claimed in claim 1. claim 4. 5 6. Fibre dyed with a dyestuffas claimed in GERHARD SCI-IRADER. 5

claim 2. WERNER ZERWECK.

